JP6253554B2 - Composite refractory and method for producing the same - Google Patents
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- 239000002131 composite material Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000011521 glass Substances 0.000 claims description 85
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 71
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 70
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 64
- 238000010304 firing Methods 0.000 claims description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 38
- 229910052710 silicon Inorganic materials 0.000 claims description 38
- 239000010703 silicon Substances 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 36
- 238000000576 coating method Methods 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 28
- 229910052796 boron Inorganic materials 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 26
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 24
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 description 40
- 230000003647 oxidation Effects 0.000 description 39
- 238000011156 evaluation Methods 0.000 description 32
- 230000000694 effects Effects 0.000 description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 19
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- 230000014759 maintenance of location Effects 0.000 description 18
- 238000013001 point bending Methods 0.000 description 17
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- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000011819 refractory material Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052863 mullite Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 238000002309 gasification Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、複合耐火物およびその製造方法に関するものである。 The present invention relates to a composite refractory and a method for producing the same.
炭化ケイ素（ＳｉＣ）を窒化ケイ素（Ｓｉ３Ｎ４）及び／又は酸窒化ケイ素（Ｓｉ２ＯＮ２）で結合させた窒化ケイ素結合ＳｉＣ耐火物は、熱伝導性や、高温下での耐久性に優れた複合耐火物として、窯道具等、各種用途に使用されている。 Silicon nitride bonded SiC refractories bonded with silicon carbide (SiC) with silicon nitride (Si 3 N 4 ) and / or silicon oxynitride (Si 2 ON 2 ) are excellent in thermal conductivity and durability at high temperatures. As an excellent composite refractory, it is used for various purposes such as kiln tools.
窒化ケイ素結合ＳｉＣ耐火物を窯道具として使用する場合、繰り返し使用すると、耐火物の酸化等に起因する劣化が発生する。このような劣化が進行して、強度低下や破損が生じた時点で、製品寿命を終えることとなる。そこで、従来から、製品寿命を延ばす対策として、窒化ケイ素結合ＳｉＣ耐火物の表面にＳｉＯ２ガラス被膜を形成する方法が一般に採用されている（例えば、特許文献１）。 When the silicon nitride bonded SiC refractory is used as a kiln tool, deterioration due to oxidation of the refractory occurs when repeatedly used. When such deterioration progresses and the strength decreases or breaks, the product life ends. Therefore, conventionally, a method of forming a SiO 2 glass coating on the surface of a silicon nitride-bonded SiC refractory has been generally employed as a measure for extending the product life (for example, Patent Document 1).
しかし、ＳｉＯ２ガラスには、その軟化点以下では、ＳｉＯ２ガラスと、基材である窒化ケイ素結合ＳｉＣとの熱膨張差に起因した微細なクラックが多数存在しており、従来のＳｉＯ２ガラス被膜を有する窒化ケイ素結合ＳｉＣ耐火物を、ＳｉＯ２ガラスの軟化点以下の温度域で使用すると、このクラックから酸素が侵入してしまい、ガラス被膜による酸化抑制効果が十分発揮されないという問題があった。 However, the SiO 2 glass, below its softening point, and SiO 2 glass, fine cracks due to the difference in thermal expansion between the silicon nitride-bonded SiC as a substrate has numerous and conventional SiO 2 glass When a silicon nitride-bonded SiC refractory having a coating is used in a temperature range below the softening point of SiO 2 glass, oxygen enters from the cracks, and there is a problem that the oxidation suppression effect by the glass coating is not fully exhibited. .
また、ＳｉＯ２ガラスを減圧・低酸素の雰囲気下におくと、ＳｉＯ２が分解されてＳｉＯガスとＯ２ガスとなって蒸発する現象が観察される。このような、低酸素の雰囲気下においても、雰囲気と接触する表面や気孔内表面では、窒化ケイ素結合ＳｉＣ耐火物中のＳｉＣやＳｉ３Ｎ４及び／又はＳｉ２ＯＮ２の酸化反応によるガラスの生成が進行するが、このとき並行して、ＳｉＯ２ガラスがＳｉＯガスとなって蒸発する現象も進行するため、生成したガラス被膜の緻密性が損なわれていく。このため、上記した従来のガラス被膜を有する窒化ケイ素結合ＳｉＣ耐火物を、減圧・低酸素の雰囲気下で使用すると、時間の経過とともに、窒化ケイ素結合ＳｉＣ耐火物の表面に生成したガラス被膜による酸化抑制効果が失われてしまうという問題があった。 In addition, when SiO 2 glass is placed in an atmosphere of reduced pressure and low oxygen, a phenomenon is observed in which SiO 2 is decomposed and evaporated into SiO gas and O 2 gas. Even in such a low-oxygen atmosphere, the surface of the glass in contact with the atmosphere or the inner surface of the pores is caused by the oxidation reaction of SiC, Si 3 N 4 and / or Si 2 ON 2 in the silicon nitride-bonded SiC refractory. Although the generation proceeds, at the same time, a phenomenon in which the SiO 2 glass becomes SiO gas and evaporates also proceeds, so that the denseness of the generated glass film is impaired. For this reason, when the silicon nitride bonded SiC refractory having the conventional glass coating described above is used in an atmosphere of reduced pressure and low oxygen, oxidation with the glass coating formed on the surface of the silicon nitride bonded SiC refractory over time. There was a problem that the suppression effect was lost.
本発明の目的は前記問題を解決し、上記の従来技術では、ガラス被膜による酸化抑制効果が得にくい条件下、具体的には、ＳｉＯ２ガラスの軟化点以下の温度域、もしくは、減圧・低酸素の雰囲気下の少なくとも何れかの条件下における窒化ケイ素結合ＳｉＣ耐火物の酸化による劣化を抑制し、製品の長寿命化を図ることができる技術を提供することである。 The object of the present invention is to solve the above-mentioned problems, and in the above-described conventional technology, under a condition where it is difficult to obtain the effect of suppressing oxidation by the glass coating, specifically, a temperature range below the softening point of SiO 2 glass, or reduced pressure / low It is an object of the present invention to provide a technique capable of suppressing deterioration due to oxidation of a silicon nitride-bonded SiC refractory under at least one of the conditions under an oxygen atmosphere and extending the product life.
本発明では、上記課題を解決するために、炭化ケイ素を、窒化ケイ素及び／又は酸窒化ケイ素で結合させた窒化ケイ素結合ＳｉＣ耐火物に、ＳｉＯ２系ガラス被膜を形成した複合耐火物において、「見掛け気孔率が１０％以下であり、化学組成として、Ａｌを０．２５〜２．４質量％かつＢを１．５超〜８．５質量％含有する」構成、もしくは、「見掛け気孔率が１０％以下であり、該複合耐火物の表面から少なくとも０．５ｍｍ深さの部分に、化学組成として、Ａｌを０．２５〜２．４質量％かつＢを１．５超〜８．５質量％含有する」構成を採用している。 In the present invention, in order to solve the above problems, in a composite refractory in which a silicon nitride-bonded SiC refractory in which silicon carbide is bonded with silicon nitride and / or silicon oxynitride is formed with a SiO 2 glass coating, The apparent porosity is 10% or less, and the chemical composition includes 0.25 to 2.4 mass% Al and more than 1.5 to 8.5 mass% B, or “the apparent porosity is 10% or less, and at least 0.5 mm deep from the surface of the composite refractory, as a chemical composition, Al is 0.25 to 2.4% by mass and B is more than 1.5 to 8.5% by mass. % Content ”is adopted.
前記ＳｉＯ２系ガラス被膜は、Ａｌ２Ｏ３とＢ２Ｏ３を含有するガラス被膜であることが好ましく、前記窒化ケイ素及び／又は酸窒化ケイ素と炭化ケイ素を、質量比＝（窒化ケイ素及び／又は酸窒化ケイ素）の質量/炭化ケイ素の質量＝０．２〜０．５の割合で含有することが好ましい。 The SiO 2 -based glass coating is preferably a glass coating containing Al 2 O 3 and B 2 O 3 , and the silicon nitride and / or silicon oxynitride and silicon carbide have a mass ratio = (silicon nitride and / or Or silicon oxynitride) / silicon carbide mass = a ratio of 0.2 to 0.5.
本発明のように、「見掛け気孔率が１０％以下であり、化学組成として、Ａｌを０．２５〜２．４質量％かつＢを１．５超〜８．５質量％含有する」構成、もしくは、「見掛け気孔率が１０％以下であり、該複合耐火物の表面から少なくとも０．５ｍｍ深さの部分に、化学組成として、Ａｌを０．２５〜２．４質量％かつＢを１．５超〜８．５質量％含有する」構成を有する「炭化ケイ素を、窒化ケイ素及び／又は酸窒化ケイ素で結合させた窒化ケイ素結合ＳｉＣ耐火物に、ＳｉＯ２系ガラス被膜を形成した複合耐火物」では、Ｂが、「硼素を含むＳｉＯ２系ガラス」を生成させる為の硼素源となり、耐火物表面や気孔内表面に、「硼素を含むＳｉＯ２系ガラス被膜」が生成される。 As in the present invention, “the apparent porosity is 10% or less, and the chemical composition contains Al in an amount of 0.25 to 2.4% by mass and B in an amount of more than 1.5 to 8.5% by mass”. Or, “The apparent porosity is 10% or less, and at least 0.5 mm from the surface of the composite refractory, the chemical composition is 0.25 to 2.4 mass% Al and 1. Composite refractory having a SiO 2 glass coating formed on a silicon nitride-bonded SiC refractory in which silicon carbide is bonded with silicon nitride and / or silicon oxynitride, having a configuration of “containing more than 5 to 8.5% by mass” ", B serves as a boron source for producing" boron-containing SiO 2 glass ", and" boron-containing SiO 2 glass coating "is produced on the surface of the refractory and in the pores.
硼素を含むＳｉＯ２系ガラスは、硼素を含まないＳｉＯ２系ガラスに比べて融点が低くなる。従来のＳｉＯ２ガラス被膜（硼素を含まないＳｉＯ２系ガラスによる被膜）では、ＳｉＯ２ガラスの軟化点以下の温度域において、ガラス被膜のクラックから酸素が侵入して、窒化ケイ素結合ＳｉＣ耐火物の酸化による劣化を促進する現象が生じていたが、本発明では、上記構成により、融点が低下するため、硼素を含まないＳｉＯ２系ガラスの軟化点以下の温度域であっても、硼素を含むＳｉＯ２系ガラスの軟化点以上の温度域であれば、前記現象を回避して酸化による劣化を抑制し、製品の長寿命化を図ることができる。また、硼素を含むＳｉＯ２系ガラスはＳｉＯ２ガラスとしての安定性が増す為、ＳｉＯ２の分解によるＳｉＯの生成、ガス化を抑制する事が出来る。なお、見掛け気孔率が１０％超となると、この酸化劣化抑制効果が得られにくくなるため、本発明では、見掛け気孔率を１０％以下として、製品の長寿命化を実現している。 The SiO 2 glass containing boron has a lower melting point than the SiO 2 glass containing no boron. In the conventional SiO 2 glass film (coating according SiO 2 -based glass not containing boron), in a temperature range below the softening point of the SiO 2 glass, oxygen from the cracking of the glass film from entering, the silicon-bonded SiC refractory nitride Although a phenomenon that promotes deterioration due to oxidation has occurred, in the present invention, the melting point is lowered due to the above-described configuration. Therefore, boron is included even in a temperature range below the softening point of SiO 2 glass not containing boron. If the temperature is higher than the softening point of the SiO 2 glass, the above phenomenon can be avoided, deterioration due to oxidation can be suppressed, and the product life can be extended. In addition, since SiO 2 glass containing boron is more stable as SiO 2 glass, it is possible to suppress generation and gasification of SiO due to decomposition of SiO 2 . Note that when the apparent porosity exceeds 10%, it becomes difficult to obtain this effect of suppressing oxidative degradation. Therefore, in the present invention, the apparent porosity is set to 10% or less, thereby realizing a long product life.
Ａｌは、硼素を含むＳｉＯ２系ガラス被膜中にムライト質（３Ａｌ２Ｏ３・２ＳｉＯ２〜２Ａｌ２Ｏ３・ＳｉＯ２）組成を生成させるための原料となる。化学組成として、Ａｌを０．２５〜２．４質量％含有する本発明の「ＳｉＯ２系ガラス被膜を有する複合耐火物」では、耐火物表面や気孔内表面に生成されるＳｉＯ２ガラス成分がムライト化するため、減圧・低酸素の雰囲気下における、ＳｉＯ２の分解およびガス化を抑制することができる。なお、本明細書において「化学組成として、」とは、「化合物や元素などの化学成分として」を意味するものであり、元素単体としての含有に限定されないことを意味するものである。 Al is a raw material for generating a mullite (3Al 2 O 3 .2SiO 2 to 2Al 2 O 3 .SiO 2 ) composition in a SiO 2 -based glass coating containing boron. In the “composite refractory having a SiO 2 -based glass coating” of the present invention containing 0.25 to 2.4 mass% of Al as a chemical composition, the SiO 2 glass component generated on the surface of the refractory or the pore inner surface is Since mullite is formed, decomposition and gasification of SiO 2 under reduced pressure and low oxygen atmosphere can be suppressed. In the present specification, “as a chemical composition” means “as a chemical component such as a compound or element”, and means not limited to inclusion as a single element.
上記の各効果が相乗的に作用する本発明によれば、ガラス被膜による酸化抑制効果が得にくい条件下、具体的には、ＳｉＯ２ガラスの軟化点以下の温度域、もしくは、減圧・低酸素の雰囲気下の少なくとも何れかの条件下における窒化ケイ素結合ＳｉＣ耐火物の酸化による劣化を抑制（具体的には、１ｈＰａのＡｒ雰囲気中において、１６００℃にて５時間暴露後の浸食深さが２８５μm以下となるレベルに抑制）し、製品の長寿命化を図ることができる。 According to the present invention in which each of the above effects acts synergistically, it is difficult to obtain the effect of suppressing oxidation by the glass coating, specifically, a temperature range below the softening point of SiO 2 glass, or reduced pressure / low oxygen. Deterioration due to oxidation of silicon nitride-bonded SiC refractories under at least one of the following conditions (specifically, the erosion depth after exposure at 1600 ° C. for 5 hours in an Ar atmosphere of 1 hPa is 285 μm) The product life can be extended by suppressing the level to the following level).
このように、製品の長寿命化を図ることにより、廃棄物の削減や、新しい窯道具への交換回数の低減による作業性の向上という効果を奏することができる。また、ＳｉＯ２の分解およびガス化を抑制することにより、ガス化成分の焼成炉内への飛散による汚染問題も回避することができる。 Thus, by prolonging the life of the product, it is possible to achieve an effect of improving workability by reducing waste and reducing the number of times of replacement with a new kiln tool. Further, by suppressing the decomposition and gasification of SiO 2 , it is also possible to avoid the problem of contamination due to scattering of gasified components into the firing furnace.
「ＳｉＯ２系ガラス被膜」を、特に、Ａｌ２Ｏ３とＢ２Ｏ３を含有するガラス被膜とすることにより、酸化によるクラックの抑制と低酸素雰囲気下でのＳｉＯ２分解抑制に著しい効果を奏し、表面のガラス被膜を強固にし、ガラス被膜の劣化を、従来技術に比べて顕著に抑制することができる。 By making the “SiO 2 glass coating” a glass coating containing Al 2 O 3 and B 2 O 3 in particular, it has a remarkable effect on suppressing cracks due to oxidation and suppressing SiO 2 decomposition under a low oxygen atmosphere. As a result, the glass coating on the surface can be strengthened and the deterioration of the glass coating can be remarkably suppressed as compared with the prior art.
以下に本発明の好ましい実施形態を示す。
本実施形態の窒化ケイ素結合ＳｉＣ耐火物は、原料調合〜混合〜成形（鋳込等）〜離型〜乾燥〜一次焼成（窒素雰囲気焼成）〜二次焼成（酸化焼成）の各工程を経て製造される。以下、各工程について説明を行う。
Preferred embodiments of the present invention are shown below.
The silicon nitride bonded SiC refractory of the present embodiment is manufactured through each process of raw material preparation, mixing, molding (casting, etc.), mold release, drying, primary firing (nitrogen atmosphere firing), and secondary firing (oxidation firing). Is done. Hereinafter, each step will be described.
（原料調合工程）
０．０５〜３０００μｍのＳｉＣを６５〜８８質量％、０．０１〜１００μｍの金属Ｓｉを９〜２０質量％含有させ、その他の原料として、Ｆｅ２Ｏ３を０．５質量％、Ａｌ２Ｏ３を０．３〜５質量％、Ｂ４Ｃを２．５〜１５質量％含有させて、原料の調合を行う。本実施形態では、焼結助剤としてＦｅ２Ｏ３を添加し、ガラス被膜を形成するガラス被膜形成物質としてＡｌ２Ｏ３、Ｂ４Ｃを添加している。ＳｉＣ粒子径が０．０５μｍ以下になると、充填密度が低くなることにより、見掛け気孔率が大きくなり本実施形態での酸化抑制効果が得られにくく、また、ＳｉＣ粒子径が３０００μｍ以上になると、見掛け気孔率は低下するが、曲げ強度の低下が大きくなり、耐火物としての必要強度が得にくくなるため、何れも好ましくない。金属Ｓｉは、窒素含有雰囲気下での焼成時に、窒化ケイ素を生成しＳｉＣ粒子間の結合を成すが、この時に粒子径が０．０１μｍ以下になると、ＳｉＣ粒子間を十分に結合することが出来ず、見掛け気孔率が大きく、かつ、低強度となり、また、１００μｍ以上の場合になると、金属Ｓｉ全体が窒化物化することが出来ず、金属Ｓｉが残留することとなり耐火物としての機能を果たさなくなるため、何れも好ましくない。
(Raw material preparation process)
0.05 to 3000 μm of SiC is contained in an amount of 65 to 88% by mass, 0.01 to 100 μm of metal Si is contained in an amount of 9 to 20% by mass, and other raw materials include 0.5% by mass of Fe 2 O 3 and Al 2 O. 3 is contained in an amount of 0.3 to 5% by mass and B 4 C is contained in an amount of 2.5 to 15% by mass to prepare a raw material. In this embodiment, Fe 2 O 3 is added as a sintering aid, and Al 2 O 3 and B 4 C are added as glass film forming substances for forming a glass film. When the SiC particle diameter is 0.05 μm or less, the packing density is lowered, and thus the apparent porosity is increased, and it is difficult to obtain the effect of suppressing oxidation in the present embodiment, and when the SiC particle diameter is 3000 μm or more, it is apparent. Although the porosity decreases, the decrease in bending strength increases and it becomes difficult to obtain the required strength as a refractory. Metal Si forms silicon nitride and forms bonds between SiC particles when fired in a nitrogen-containing atmosphere. If the particle diameter is 0.01 μm or less at this time, SiC particles can be sufficiently bonded. In addition, when the apparent porosity is large and the strength is low, and when the thickness is 100 μm or more, the entire metal Si cannot be nitrided, and the metal Si remains and does not function as a refractory. Therefore, neither is preferable.
（混合工程）
混合工程では、上記の原料調合工程で調合した原料に、水、バインダー、分散剤等を添加して混合して坏土を製作、もしくはスラリー化させる。
(Mixing process)
In the mixing step, water, a binder, a dispersant and the like are added to the raw material prepared in the raw material preparation step and mixed to produce or slurry the clay.
（成形工程〜離型工程〜乾燥工程）
成形工程では、上記の混合工程で得られた坏土もしくはスラリーを使用し、モールド内での圧力成形、鋳込み成形等、任意の成形方法で、所望の形状に成形し、所定時間経過後、離形および乾燥を行う。
(Molding process-mold release process-drying process)
In the molding process, the clay or slurry obtained in the above mixing process is used, molded into a desired shape by an arbitrary molding method such as pressure molding or casting in a mold, and separated after a predetermined time. Form and dry.
（一次焼成（窒素雰囲気焼成）工程）
上記の乾燥工程を経た成形体を、窒素含有雰囲気下において焼成する。ここで、窒素含有雰囲気における窒素濃度としては、９０％以上が好ましく、９９％以上が更に好ましい。焼成温度は、その最高保持温度が通常１１００〜１５００℃の範囲、好ましくは１３００〜１４５０℃の範囲であり、焼成時間としては５〜３０ｈｒが適当である。窒素含有雰囲気下での焼成により、成形体中のＳｉと雰囲気中の窒素との反応が生じ、窒化ケイ素が、骨材（ＳｉＣ粒子）の粒界に生成される。これにより、骨材同士を窒化ケイ素及び／又は酸窒化ケイ素で結合させた窒化ケイ素結合ＳｉＣ耐火物が得られる。
(Primary firing (nitrogen atmosphere firing) step)
The molded body that has undergone the drying step is fired in a nitrogen-containing atmosphere. Here, the nitrogen concentration in the nitrogen-containing atmosphere is preferably 90% or more, and more preferably 99% or more. The firing temperature is usually in the range of 1100 to 1500 ° C., preferably 1300 to 1450 ° C., and the firing time is suitably 5 to 30 hours. By firing in a nitrogen-containing atmosphere, a reaction between Si in the molded body and nitrogen in the atmosphere occurs, and silicon nitride is generated at the grain boundaries of the aggregate (SiC particles). Thereby, a silicon nitride bonded SiC refractory in which the aggregates are bonded with silicon nitride and / or silicon oxynitride is obtained.
（二次焼成（酸化焼成）工程）
本実施形態では、上記の一次焼成工程で得られた焼成体を、更に、酸素濃度４〜１０％、焼成温度１３００〜１６００℃、最高温度保持時間５〜１５時間の条件で焼成する。当該条件下での焼成により、耐火物表面にガラス被膜が形成され、酸化等に起因する劣化を抑制することができる。
(Secondary firing (oxidation firing) step)
In this embodiment, the fired body obtained in the primary firing step is further fired under conditions of an oxygen concentration of 4 to 10%, a firing temperature of 1300 to 1600 ° C., and a maximum temperature holding time of 5 to 15 hours. By baking under the conditions, a glass film is formed on the surface of the refractory, and deterioration due to oxidation or the like can be suppressed.
本実施形態では、上記のように、原料にＢ４Ｃを含有させており、Ｂは、耐火物表面や気孔内表面に、硼素を含むＳｉＯ２系ガラス被膜を生成させる為の硼素源となる。このため、二次焼成時には、耐火物表面や気孔内表面に、硼素を含むＳｉＯ２系ガラス被膜が生成される。硼素を含むＳｉＯ２系ガラスは、ＳｉＯ２ガラスに比べて融点が低くなる。 In the present embodiment, as described above, B 4 C is contained in the raw material, and B serves as a boron source for generating a SiO 2 -based glass coating containing boron on the surface of the refractory or the pore inner surface. . For this reason, during the secondary firing, a SiO 2 -based glass coating containing boron is generated on the surface of the refractory or the pore inner surface. The SiO 2 glass containing boron has a lower melting point than SiO 2 glass.
背景技術の欄にも記載のように、ＳｉＯ２ガラスには、その軟化点以下では、ＳｉＯ２ガラスと、基材である窒化ケイ素結合ＳｉＣとの熱膨張差に起因した微細なクラックが多数存在しており、従来のＳｉＯ２ガラス被膜を有する窒化ケイ素結合ＳｉＣ耐火物を、ＳｉＯ２ガラスの軟化点以下の温度域で使用すると、このクラックから酸素が侵入してしまい、ガラス被膜による酸化抑制効果が十分発揮されないという問題があったのに対し、本発明では、ＳｉＯ２ガラスに比べて融点の低い「硼素を含むＳｉＯ２系ガラス」を用いてガラス被膜を形成しているため、ＳｉＯ２ガラスの軟化点以下の温度域であっても、Ｂ２Ｏ３ガラスの軟化点以上の温度域での使用であれば、クラックの封止効果を得ることができる。また、従来のＳｉＯ２ガラス被膜では、ＳｉＯ２ガラスの軟化点以下の温度域において、ガラス被膜のクラックから酸素が侵入する現象が生じていたが、本発明のように、原料にＢ４Ｃを含有させて、二次焼成時に、硼素を含むＳｉＯ２系ガラス被膜を生成させることにより、硼素を含むＳｉＯ２系ガラスの軟化点以下の温度域におけるガラス被膜のクラックからの酸素の侵入を回避することができる。 As described in the Background Art section, SiO 2 glass has many fine cracks due to the difference in thermal expansion between the SiO 2 glass and the silicon nitride-bonded SiC as the base material below the softening point. If a silicon nitride-bonded SiC refractory having a conventional SiO 2 glass coating is used in a temperature range below the softening point of the SiO 2 glass, oxygen enters from these cracks, and the oxidation suppression effect by the glass coating since whereas there is a problem that not sufficiently exhibited, in the present invention, as compared to SiO 2 glass so as to form a glass coat with a "SiO 2 glass containing boron" low melting point, SiO 2 glass Even if it is a temperature range below the softening point, if it is used in a temperature range above the softening point of the B 2 O 3 glass, a crack sealing effect can be obtained. Further, in the conventional SiO 2 glass coating, a phenomenon in which oxygen enters from cracks in the glass coating occurs in a temperature range below the softening point of the SiO 2 glass. However, as in the present invention, B 4 C is used as a raw material. By making it contain and generating a SiO 2 -based glass coating containing boron at the time of secondary firing, invasion of oxygen from cracks in the glass coating in the temperature range below the softening point of the SiO 2 -based glass containing boron is avoided. be able to.
なお、Ｂの量が１．５質量％より少ない場合は、ＳｉＯ２ガラスの軟化点が十分に下がらず、微細なクラックが多く発生するため好ましくない。Ｂの量が８．５質量％より多い場合は、生成させたＳｉＯ２ガラスの融点が低下しすぎるために、使用できる温度範囲が制限されるため好ましくない。 In addition, when the amount of B is less than 1.5% by mass, the softening point of the SiO 2 glass is not sufficiently lowered, and many fine cracks are generated, which is not preferable. When the amount of B is more than 8.5% by mass, the melting point of the generated SiO 2 glass is excessively lowered, so that the usable temperature range is limited.
また、本実施形態では、上記のように、原料にＡｌ２Ｏ３を含有させており、Ａｌは、耐火物表面や気孔内表面にムライト質（３Ａｌ２Ｏ３・２ＳｉＯ２〜２Ａｌ２Ｏ３・ＳｉＯ２）組成を生成させるための原料となる。このため、二次焼成時に、耐火物表面や気孔内表面に生成してくるＳｉＯ２ガラス成分（前記化学組成の窒化ケイ素結合ＳｉＣ耐火物の成分に由来した酸化物からなるガラス成分）をムライト化させ、硼素を含むＳｉＯ２系ガラス被膜中にムライト相を形成させることで、減圧・低酸素の雰囲気下における、ＳｉＯ２の分解およびガス化を抑制し、ガラス被膜による保護効果を継続的に維持することができる。 In the present embodiment, as described above, Al 2 O 3 is contained in the raw material, and Al is mullite (3Al 2 O 3 .2SiO 2 to 2Al 2 O 3 on the surface of the refractory or the pores. · SiO 2) as a raw material for producing the composition. For this reason, during secondary firing, the SiO 2 glass component (glass component consisting of oxides derived from the silicon nitride-bonded SiC refractory component of the above chemical composition) formed on the surface of the refractory and the pore inner surface is converted into mullite. By forming a mullite phase in the SiO 2 glass coating containing boron, the decomposition and gasification of SiO 2 is suppressed in a reduced pressure and low oxygen atmosphere, and the protective effect of the glass coating is continuously maintained. can do.
化学組成としてＡｌが０．２５質量％より少ない場合は、ムライト相の生成量が少なくなるため、ＳｉＯ２の分解抑制効果が発揮できなくなるため好ましくない。Ａｌが２．４質量％より多い場合は過剰にムライト結晶が生成し、表面のガラス被膜が結晶化し、結晶粒界が生じることで、この粒界部分からクラックが進展し、結果としてＳｉＯ２の分解が加速する不具合があるため好ましくない。 When the chemical composition is less than 0.25% by mass, the amount of mullite phase generated is reduced, and the effect of suppressing the decomposition of SiO 2 cannot be exhibited. When Al is more than 2.4% by mass, excessive mullite crystals are generated, the glass film on the surface is crystallized, and a crystal grain boundary is generated, so that cracks develop from the grain boundary part, and as a result, SiO 2 This is not preferable because there is a problem that decomposition is accelerated.
本実施形態によれは、上記の相乗効果により、ガラス被膜による酸化抑制効果が得にくい条件下、具体的には、ＳｉＯ２ガラスの軟化点以下の温度域、もしくは、減圧・低酸素の雰囲気下の少なくとも何れかの条件下における窒化ケイ素結合ＳｉＣ耐火物の酸化による劣化を抑制し、製品の長寿命化を図ることができる。 According to the present embodiment, due to the above-mentioned synergistic effect, it is difficult to obtain an oxidation suppressing effect by the glass coating, specifically, in a temperature range below the softening point of SiO 2 glass, or in an atmosphere of reduced pressure and low oxygen. Deterioration due to oxidation of the silicon nitride-bonded SiC refractory under at least one of the conditions can be suppressed, and the product life can be extended.
更に、本実施形態では、前記のように、酸素濃度４〜１０％、焼成温度１３００〜１６００℃、最高温度保持時間５〜１５時間の条件で焼成を行うことにより、二次焼成工程における重量増加率を０．３〜１％の範囲にコントロールしている。二次焼成工程における重量増加率が１％超となるような、過剰な酸化が生じた場合、基材内部にまで、酸化が進行し、基材内部の気孔内でも酸化物が生成される。気孔内に生成したシリカ系ガラスの酸化物は、被焼成物の成分や使用環境の影響により結晶化が促進される。この結晶化（特にクリストバライト化）に伴い、基材に熱膨張・収縮が生じると、基材の組織破壊が発生しやすくなるため、製品寿命の観点から、基材内部の気孔内における酸化物の生成は好ましくない。一方、二次焼成工程における重量増加率が０．３％に満たない場合、ガラス被膜の形成が不十分となり、ガラス被膜による十分な保護効果を得る事ができない。 Furthermore, in this embodiment, as described above, the weight increase in the secondary firing step is performed by firing under conditions of an oxygen concentration of 4 to 10%, a firing temperature of 1300 to 1600 ° C., and a maximum temperature holding time of 5 to 15 hours. The rate is controlled in the range of 0.3 to 1%. When excessive oxidation occurs such that the weight increase rate in the secondary firing step exceeds 1%, the oxidation proceeds to the inside of the base material, and an oxide is generated in the pores inside the base material. The crystallization of the silica-based glass oxide generated in the pores is promoted by the influence of the components of the object to be fired and the use environment. With this crystallization (especially cristobalite formation), if thermal expansion / contraction occurs in the base material, the base material tends to break down the structure. Therefore, from the viewpoint of product life, the oxide in the pores inside the base material Production is not preferred. On the other hand, when the rate of weight increase in the secondary firing step is less than 0.3%, the formation of the glass film becomes insufficient, and a sufficient protective effect by the glass film cannot be obtained.
なお、本実施形態では、原料調合工程でＢ４Ｃを添加し、製造された窒化ケイ素結合ＳｉＣ耐火物全体の化学組成として、Ａｌを０．２５〜２．４質量％、Ｂを１．５超〜８．５質量％含有するものとしているが、本発明の窒化ケイ素結合ＳｉＣ耐火物は、複合耐火物の表面から少なくとも０．５ｍｍ深さの部分に、化学組成として、Ａｌを０．２５〜２．４質量％かつＢを１．５超〜８．５質量％含有するものであればよい。例えば、他の実施形態として、ＳｉＣを６５〜８８質量％、Ｓｉを９〜２０質量％含有させた原料を混合して、窒素雰囲気下での一次焼成した後、基材表面に、固形分として、Ｂ４Ｃを２．５〜１５質量％、Ａｌ２Ｏ３を０．５〜１０質量％含有させたスラリーを用いてコーティング処理を行い、その後、前記条件下で二次焼成を行って本発明の窒化ケイ素結合ＳｉＣ耐火物を製造することができる。さらに、他の実施形態として、ＳｉＣを６５〜８８質量％、Ｓｉを９〜２０質量％、Ｂ４Ｃを２．５〜１５質量％含有させた原料を混合して、窒素雰囲気下での一次焼成した後、更に、基材表面に、固形分として、Ｂ４Ｃを２．５〜１５質量％含有させたスラリーを用いてコーティング処理を行い、その後、前記条件下で二次焼成を行って本発明の窒化ケイ素結合ＳｉＣ耐火物を製造することもできる。 In the present embodiment, B 4 C is added in the raw material preparation step, and the chemical composition of the manufactured silicon nitride-bonded SiC refractory as a whole is 0.25 to 2.4 mass% for Al and 1.5 for B. Although it is assumed that the content is super-8.5% by mass, the silicon nitride-bonded SiC refractory of the present invention has a chemical composition of Al of 0.25 at a depth of at least 0.5 mm from the surface of the composite refractory. What is necessary is just to contain -2.4 mass% and B more than 1.5-8.5 mass%. For example, as another embodiment, after mixing raw materials containing 65 to 88% by mass of SiC and 9 to 20% by mass of Si and performing primary firing in a nitrogen atmosphere, , B 4 C is coated with a slurry containing 2.5 to 15% by mass and Al 2 O 3 is contained in an amount of 0.5 to 10% by mass, and then subjected to secondary firing under the above conditions. Inventive silicon nitride bonded SiC refractories can be produced. Furthermore, as another embodiment, a raw material containing 65 to 88% by mass of SiC, 9 to 20% by mass of Si, and 2.5 to 15% by mass of B 4 C is mixed, and is primary in a nitrogen atmosphere. After firing, the base material surface is further coated with a slurry containing 2.5 to 15% by mass of B 4 C as a solid content, and then subjected to secondary firing under the above conditions. The silicon nitride bonded SiC refractory of the present invention can also be produced.
上記の各工程を経て製造された窒化ケイ素結合ＳｉＣ耐火物は、具体的には、温度１４００〜１５００℃、酸素濃度１０００ｐｐｍ以下、圧力１０１３ｈＰａの条件下での使用に適した耐火物であり、当該条件下で、酸化劣化を効果的に回避することができる。 Specifically, the silicon nitride-bonded SiC refractory manufactured through each of the above steps is a refractory suitable for use under conditions of a temperature of 1400 to 1500 ° C., an oxygen concentration of 1000 ppm or less, and a pressure of 1013 hPa. Under conditions, oxidative degradation can be effectively avoided.
当該窒化ケイ素結合ＳｉＣ耐火物は、骨材である炭化ケイ素を結合させる骨材結合部の主成分が窒化ケイ素及び／又は酸窒化ケイ素であり、ＳｉＣの含有量が６５〜８０％、Ｓｉ３Ｎ４及び／又はＳｉ２ＯＮ２の含有量が１４〜２７％であり、その他の化学成分として、Ａｌを０．２５〜２．４質量％以下、Ｂを１．５超〜８．５質量％含有させている。その表面には、前記耐火物の成分に由来した酸化物からなるＳｉＯ２系のガラス被膜を有し、曲げ強度は３０ＭＰａ〜２００ＭＰａ、見掛け気孔率は１０％以下、嵩比重は２．６０〜２．８５となっている。 In the silicon nitride-bonded SiC refractory, the main component of the aggregate bonding portion for bonding the silicon carbide as the aggregate is silicon nitride and / or silicon oxynitride, the content of SiC is 65 to 80%, and Si 3 N 4 and / or Si 2 ON 2 content is 14 to 27%, and as other chemical components, Al is 0.25 to 2.4% by mass or less, and B is more than 1.5 to 8.5% by mass. It is included. On its surface, it has a SiO 2 glass coating made of an oxide derived from the refractory component, has a bending strength of 30 MPa to 200 MPa, an apparent porosity of 10% or less, and a bulk specific gravity of 2.60 to 2 .85.
ガラス被膜による酸化防止効果は、ガラスの融点が、耐火物の使用温度よりも若干低いレベルにあることで奏されるものである。ここで、Ａｌは、ガラスの融点を上昇させる作用を持つため、２．４質量％以上含有させると、ガラスの融点が上昇し、上記温度条件下で、前記の効果を奏することができなくなるため好ましくない。なお、Ｂは、ガラスの融点を低下させる作用を持つため、Ｂの含有量を更に増加させることにより、化学組成として、Ａｌの含有量を２．４質量％以上とすることも考えられるが、Ｂの含有量を８．５質量％超とすると、耐火物の密度が低下して、求められる耐火物強度を満たさなくなる。一方、Ｂの含有量が１．５質量％未満では、アルミと硼素を含むＳｉＯ２系ガラスの形成による本発明の効果を十分奏することができない。本発明では、化学組成として、Ａｌを０．２５〜２．４質量、かつ、Ｂを１．５超〜８．５質量％含有させることにより、上記のバランスを最適に保ち、耐火物強度を維持しつつ酸化防止効果を備える耐火物を実現している。 The anti-oxidation effect by the glass coating is achieved when the melting point of the glass is at a level slightly lower than the use temperature of the refractory. Here, since Al has an action of increasing the melting point of the glass, when 2.4% by mass or more is contained, the melting point of the glass is increased, and the above effect cannot be achieved under the above temperature condition. It is not preferable. In addition, since B has the effect | action which lowers | hangs melting | fusing point of glass, it is also considered that content of Al is made into 2.4 mass% or more as a chemical composition by further increasing the content of B, When the content of B exceeds 8.5% by mass, the density of the refractory is lowered and the required refractory strength is not satisfied. On the other hand, when the content of B is less than 1.5% by mass, the effect of the present invention due to the formation of SiO 2 glass containing aluminum and boron cannot be sufficiently achieved. In the present invention, as a chemical composition, Al is contained in an amount of 0.25 to 2.4 mass%, and B is contained in an amount of more than 1.5 to 8.5 mass%, whereby the above balance is optimally maintained and the refractory strength is increased. A refractory with an antioxidant effect is realized while maintaining it.
以下の実施例Ａでは「耐火物全体」の化学組成におけるＡｌ含有量とＢの含有量と見掛け気孔率が「耐酸化性能評価」に及ぼす影響に関する検討を行い、実施例Ｂでは「複合耐火物の表面から少なくとも０．５ｍｍ深さの部分」の化学組成におけるＡｌ含有量とＢの含有量と見掛け気孔率が「耐酸化性能評価」に及ぼす影響に関する検討を行い、実施例Ｃでは、「窒化ケイ素結合ＳｉＣ耐火物の原料として使用するＳｉＣおよび金属Ｓｉの粒径」が「耐酸化性能評価」に及ぼす影響に関する検討を行い、実施例Ｄでは二次焼成条件が「耐酸化性能評価」に及ぼす影響に関する検討を行った。 In Example A below, the influence of the Al content, B content and apparent porosity on the “oxidation resistance evaluation” in the chemical composition of “whole refractory” is examined. In Example B, “composite refractory” The effect of the Al content, the B content and the apparent porosity on the “oxidation resistance evaluation” in the chemical composition “at least 0.5 mm deep from the surface of the surface” was examined. The effect of the SiC and metal Si particle sizes used as raw materials for the silicon-bonded SiC refractory on the “oxidation resistance performance evaluation” is examined. In Example D, the secondary firing condition affects the “oxidation resistance performance evaluation”. The effect was examined.
実施例Ａ：「耐火物全体」の化学組成におけるＡｌ含有量とＢの含有量と見掛け気孔率が「耐酸化性能評価」に及ぼす影響に関する検討
（製造）
下記表１に示す各配合で原料調合、成形を行い、一次焼成（窒素濃度１００％、１４３０℃、６ｈｒ）行った後、酸素濃度８％、焼成温度１４００℃、最高温度保持時間９時間の条件下で二次焼成を行って窒化ケイ素結合ＳｉＣ耐火物を製造した（実施例１〜１３、比較例１〜５）。
（耐火物の成分分析）
製造後、各窒化ケイ素結合ＳｉＣ耐火物の成分分析を行い、Ａｌ、Ｂの含有量および、Ｓｉ３Ｎ４/ＳｉＣ比を調べた結果を、下記表１に示している。成分分析はＪＩＳ Ｒ２０１１に準拠して実施した。
（物性測定）
また、下記表１には、製造後、各窒化ケイ素結合ＳｉＣ耐火物の嵩比重、見掛け気孔率、３点曲げ強度、および、二次焼成工程における重量増加率を測定した結果も示している。嵩比重、見掛け気孔率、はＪＩＳ Ｒ２２０５の煮沸法に準拠して測定した。３点曲げ強度の測定は、ＪＩＳ Ｒ１６０１に準拠して行った。
（耐酸化性能評価）
更に、下記表１には、製造後、各窒化ケイ素結合ＳｉＣ耐火物の酸化による劣化を評価するために、各耐火物を、１ｈＰａのＡｒ雰囲気中に、温度１６００℃で５ｈｒ曝露し、「曝露中の重量減少率」および「浸食深さ」および「粒子保持性」および再度「曲げ強度（以下、評価後３点曲げ強度、という）」を測定した結果も示している。
「曝露中の重量減少率」の測定は、試験前後での変化率を算出して行った。「曝露中の重量減少率」により、組織の分解、浸食による重量変化を評価することができる。
「浸食深さ」の測定は、テストピース５０＊５０＊８ｍｍの断面組織を電子顕微鏡で観察し、窒化ケイ素結合ＳｉＣ耐火物の健全部と浸食部（図１参照）で、表層からの分解・浸食深さを測定して行った。
「粒子保持性」の測定は、耐火物の表層に粘着テープを張り付け、これを引き剥がした時に付着する５０μm以上のＳｉＣ粗粒の粒子数を２ｍｍ四方の範囲で数えて行った。 「粒子保持性」は、結合相の浸食による粒子保持性の低下を評価する指標となる。粘着テープは日本電子(株)製カーボン両面テープ Ｐ／Ｎ７８０００４５２３ を用いて、５０ｇ／ｃｍ２で１０秒間押さえた後、引き剥して上記測定を行った。
「評価後３点曲げ強度」の測定は、ＪＩＳ Ｒ１６０１に準拠して行った。
Example A: Study on the effects of Al content, B content and apparent porosity on "oxidation resistance evaluation" in the chemical composition of "whole refractory" (manufacturing)
The raw materials were prepared and molded with each formulation shown in Table 1 below, and after primary firing (nitrogen concentration 100%, 1430 ° C., 6 hours), oxygen concentration 8%, firing temperature 1400 ° C., maximum temperature holding time 9 hours. Secondary firing was performed below to produce silicon nitride-bonded SiC refractories (Examples 1 to 13 and Comparative Examples 1 to 5).
(Component analysis of refractories)
Table 1 below shows the results of component analysis of each silicon nitride-bonded SiC refractory after the production, and investigation of the contents of Al and B and the Si3N4 / SiC ratio. Component analysis was performed in accordance with JIS R2011.
(Physical property measurement)
Table 1 below also shows the results of measuring the bulk specific gravity, apparent porosity, three-point bending strength, and weight increase rate in the secondary firing step of each silicon nitride-bonded SiC refractory after production. The bulk specific gravity and the apparent porosity were measured according to the boiling method of JIS R2205. The three-point bending strength was measured according to JIS R1601.
(Oxidation resistance evaluation)
Further, in Table 1 below, in order to evaluate the deterioration of each silicon nitride-bonded SiC refractory due to oxidation after production, each refractory was exposed in an Ar atmosphere of 1 hPa at a temperature of 1600 ° C. for 5 hours. Also shown are the results of measuring the "weight reduction rate", "erosion depth", "particle retention" and "bending strength (hereinafter referred to as 3-point bending strength after evaluation)".
The “weight loss rate during exposure” was measured by calculating the rate of change before and after the test. By “weight reduction rate during exposure”, it is possible to evaluate weight change due to tissue degradation and erosion.
“Erosion depth” is measured by observing the cross-sectional structure of the test piece 50 * 50 * 8 mm with an electron microscope, and by disassembling / disassembling the surface of the silicon nitride-bonded SiC refractory from the surface and the erosion part (see FIG. 1). This was done by measuring the erosion depth.
The measurement of “particle retention” was carried out by counting the number of SiC coarse particles of 50 μm or more adhering to the surface of the refractory material when an adhesive tape was attached to the surface of the refractory and peeling it in a 2 mm square range. “Particle retention” is an index for evaluating the decrease in particle retention due to erosion of the binder phase. The pressure-sensitive adhesive tape was carbon double-sided tape P / N780004523 manufactured by JEOL Ltd., pressed at 50 g / cm 2 for 10 seconds, and then peeled off to perform the above measurement.
The “3-point bending strength after evaluation” was measured according to JIS R1601.
（実施例Ａの考察）
「耐火物全体」の化学組成として、Ａｌを０．２５〜２．４質量％、Ｂを１．５超〜８．５質量％含有し、かつ、見掛け気孔率が１０％以下である実施例１〜８では、「曝露中の重量減少率」を７．８４％以下、「浸食深さ」を３５５μｍ以下、「粒子保持性」測定における粘着テープへの付着数を４０以下に、各々、抑制されることでき、「評価後３点曲げ強度」は、１１０ＭＰａ以上に維持されることが確認された。
見掛け気孔率が１０％超である比較例１および比較例４では、「曝露中の重量減少率」が１０％超、「浸食深さ」が４８０μｍ以上、「粒子保持性」測定における粘着テープへの付着数が２２３以上となり、「評価後３点曲げ強度」は、７８ＭＰａ以下にまで低下し、上記実施例１〜８と比べて、耐酸化性能が劣ることが確認された。
Ｂの含有量が１．５質量％未満の比較例２およびＢの含有量が８．５質量％超の比較例５では、何れも、「曝露中の重量減少率」が９％超、「浸食深さ」が６５０μｍ以上、「粒子保持性」測定における粘着テープへの付着数が１９６以上となり、「評価後３点曲げ強度」は、８２ＭＰａ以下にまで低下し、上記実施例１〜８と比べて、耐酸化性能が劣ることが確認された。
Ａｌの含有量が０．２５質量％未満の比較例３およびＡｌの含有量が２．４質量％超の比較例６、７では、何れも、「曝露中の重量減少率」が９％超、「浸食深さ」が５９０μｍ以上、「粒子保持性」測定における粘着テープへの付着数が１８０以上となり、「評価後３点曲げ強度」は、１０１ＭＰａ以下にまで低下し、上記実施例１〜８と比べて、耐酸化性能が劣ることが確認された。
Ａｌの含有量が２．４質量％超で、かつ、Ｓｉ３Ｎ４/ＳｉＣ比率でＳｉ３Ｎ４成分が０．５超の比較例８では、「評価後３点曲げ強度」は実施例と同程度に良好な結果（１２２ＭＰａ）を示すが、「曝露中の重量減少率」が１０．２％、「浸食深さ」が８８５μｍ、「粒子保持性」測定における粘着テープへの付着数が２６３となり、上記実施例１〜８と比べて、耐食性が得にくいことが確認された。
(Consideration of Example A)
Example of chemical composition of “whole refractory” containing 0.25 to 2.4 mass% Al, more than 1.5 to 8.5 mass% B and having an apparent porosity of 10% or less In 1 to 8, “weight reduction rate during exposure” is 7.84% or less, “erosion depth” is 355 μm or less, and the number of adhesion to adhesive tape in “particle retention” measurement is 40 or less, respectively. It was confirmed that the “three-point bending strength after evaluation” was maintained at 110 MPa or more.
In Comparative Example 1 and Comparative Example 4 in which the apparent porosity is more than 10%, the “weight reduction rate during exposure” is more than 10%, the “erosion depth” is 480 μm or more, and the adhesive tape in the “particle retention” measurement. The adhesion number of 223 was 223 or more, and the “three-point bending strength after evaluation” was reduced to 78 MPa or less, and it was confirmed that the oxidation resistance performance was inferior compared with Examples 1-8.
In Comparative Example 2 in which the B content is less than 1.5% by mass and Comparative Example 5 in which the B content is more than 8.5% by mass, the “weight reduction rate during exposure” exceeds 9%. The “erosion depth” is 650 μm or more, the number of adhesion to the adhesive tape in the “particle retention” measurement is 196 or more, and the “three-point bending strength after evaluation” is reduced to 82 MPa or less. In comparison, it was confirmed that the oxidation resistance was inferior.
In Comparative Example 3 in which the Al content is less than 0.25% by mass and Comparative Examples 6 and 7 in which the Al content exceeds 2.4% by mass, the “weight reduction rate during exposure” exceeds 9%. The “erosion depth” is 590 μm or more, the number of adhesion to the adhesive tape in the “particle retention” measurement is 180 or more, and the “three-point bending strength after evaluation” is reduced to 101 MPa or less. Compared to 8, it was confirmed that the oxidation resistance performance was inferior.
In Comparative Example 8 in which the Al content exceeds 2.4 mass% and the Si 3 N 4 component exceeds Si 0.5 in the Si 3 N 4 / SiC ratio, the “three-point bending strength after evaluation” is As good as (122 MPa), the “weight reduction rate during exposure” is 10.2%, the “erosion depth” is 885 μm, and the number of adhesion to the adhesive tape in the “particle retention” measurement is 263, confirming that it was difficult to obtain corrosion resistance as compared with Examples 1 to 8 above.
実施例Ｂ：「複合耐火物の表面から０．５ｍｍ深さ間の部分」の化学組成におけるＡｌ含有量とＢの含有量と見掛け気孔率が「耐酸化性能評価」に及ぼす影響に関する検討
（製造）
ＳｉＣを６５〜８８質量％、Ｓｉを９〜２０質量％含有させた原料を混合して、窒素雰囲気下での一次焼成した後、基材表面に、固形分として、Ｂ４ＣとＡｌ２Ｏ３とＳｉＯ２を下記表２に示す割合で含有するスラリーを用いてコーティング処理を行い、その後、酸素濃度８％、焼成温度１４００℃、最高温度保持時間９時間の条件下で二次焼成を行って窒化ケイ素結合ＳｉＣ耐火物を製造した（実施例９〜１４、比較例９〜１４）。
（耐火物の成分分析）
製造後、各窒化ケイ素結合ＳｉＣ耐火物の複合耐火物の表面から０．５ｍｍ深さまでの部分をサンプリングして成分分析を行い、Ａｌ、Ｂの含有量および、Ｓｉ３Ｎ４/ＳｉＣ比を調べた結果を、下記表２に示している。成分分析はＪＩＳ Ｒ２０１１に準拠して実施した。
（物性測定）および（耐酸化性能評価）は、上記実施例Ａと同様に行い、その結果を下記表２に示している。
Example B: Study on the effect of Al content, B content and apparent porosity on the "oxidation resistance evaluation" in the chemical composition of "the portion between 0.5 mm depth from the surface of the composite refractory" (manufacturing) )
After mixing raw materials containing 65 to 88% by mass of SiC and 9 to 20% by mass of Si and performing primary firing in a nitrogen atmosphere, B 4 C and Al 2 O as solids on the substrate surface 3 and SiO 2 were coated using a slurry containing the proportions shown in Table 2 below, followed by secondary firing under conditions of an oxygen concentration of 8%, a firing temperature of 1400 ° C., and a maximum temperature holding time of 9 hours. Thus, silicon nitride-bonded SiC refractories were produced (Examples 9 to 14 and Comparative Examples 9 to 14).
(Component analysis of refractories)
After the production, the components from the surface of each silicon nitride-bonded SiC refractory to a depth of 0.5 mm from the composite refractory were sampled and subjected to component analysis, and the results of examining the contents of Al and B and the Si3N4 / SiC ratio were as follows. It is shown in Table 2 below. Component analysis was performed in accordance with JIS R2011.
(Physical property measurement) and (Oxidation resistance evaluation) were performed in the same manner as in Example A, and the results are shown in Table 2 below.
（実施例Ｂの考察）
「複合耐火物の表面から０．５ｍｍ深さ間の部分」の化学組成として、Ａｌを０．２５〜２．４質量％、Ｂを１．５超〜８．５質量％含有し、かつ、見掛け気孔率が１０％以下である実施例９〜１４では、「曝露中の重量減少率」を６．８％以下、「浸食深さ」を２９０μｍ以下、「粒子保持性」測定における粘着テープへの付着数を３３以下に、各々、抑制されすることができ、「評価後３点曲げ強度」は、１３５ＭＰａ以上に維持されることが確認された。
Ｂの含有量が１．５質量％未満の比較例９およびＢの含有量が８．５質量％超の比較例１２では、何れも、「曝露中の重量減少率」が８．９％以上、「浸食深さ」が６０２μｍ以上、「粒子保持性」測定における粘着テープへの付着数が７１以上となり、「評価後３点曲げ強度」は、１２０ＭＰａ以下にまで低下し、上記実施例９〜１４と比べて、耐酸化性能が劣ることが確認された。
Ａｌの含有量が０．２５質量％未満の比較例１０およびＡｌの含有量が２．４質量％超の比較例１１、１３、１４では、何れも、「曝露中の重量減少率」が１１．６％以上、「浸食深さ」が７０２μｍ以上、「粒子保持性」測定における粘着テープへの付着数が８７以上となり、「評価後３点曲げ強度」は、１１９ＭＰａ以下にまで低下し、上記実施例１〜８と比べて、耐酸化性能が劣ることが確認された。
(Consideration of Example B)
As a chemical composition of “the portion between 0.5 mm depth from the surface of the composite refractory”, Al is contained in an amount of 0.25 to 2.4 mass%, B is contained in an amount of more than 1.5 to 8.5 mass%, and In Examples 9 to 14 where the apparent porosity is 10% or less, the “weight reduction rate during exposure” is 6.8% or less, the “erosion depth” is 290 μm or less, and the adhesive tape in the “particle retention” measurement It was confirmed that the adhesion number of each was suppressed to 33 or less, and the “three-point bending strength after evaluation” was maintained at 135 MPa or more.
In Comparative Example 9 in which the B content is less than 1.5% by mass and Comparative Example 12 in which the B content exceeds 8.5% by mass, the “weight reduction rate during exposure” is 8.9% or more. The “erosion depth” is 602 μm or more, the number of adhesion to the adhesive tape in the “particle retention” measurement is 71 or more, and the “three-point bending strength after evaluation” is reduced to 120 MPa or less. Compared to 14, it was confirmed that the oxidation resistance performance was inferior.
In Comparative Example 10 in which the Al content is less than 0.25% by mass and Comparative Examples 11, 13, and 14 in which the Al content exceeds 2.4% by mass, the “weight reduction rate during exposure” is 11 .6% or more, “erosion depth” is 702 μm or more, the number of adhesion to the adhesive tape in the “particle retention” measurement is 87 or more, and “three-point bending strength after evaluation” is reduced to 119 MPa or less. Compared with Examples 1-8, it was confirmed that oxidation resistance performance is inferior.
実施例Ｃ：「窒化ケイ素結合ＳｉＣ耐火物の原料として使用するＳｉＣおよび金属Ｓｉの粒径」が「耐酸化性能評価」に及ぼす影響に関する検討
（製造）
下記表３に示す各配合で原料調合、成形を行い、一次焼成（窒素濃度１００％、１４３０℃、６ｈｒ）行った後、酸素濃度８％、焼成温度１４００℃、最高温度保持時間９時間の条件下で二次焼成を行って窒化ケイ素結合ＳｉＣ耐火物を製造した（実施例１５〜１７、比較例１６〜１７）。
（耐火物の成分分析、物性測定および耐酸化性能評価）
上記実施例Ａと同様に、耐火物の成分分析、および、物性測定、および耐酸化性能評価を行った結果を下記表３に示している。なお、表３には、二次焼成での重量変化（酸化重量変化率）を調べた結果も示している。
Example C: Study on the Effect of “Grain Size of SiC and Metal Si Used as Raw Materials for Silicon Nitride Bonded SiC Refractory” on “Oxidation Resistance Evaluation” (Manufacturing)
The raw materials were prepared and molded with each formulation shown in Table 3 below, and after primary firing (nitrogen concentration 100%, 1430 ° C., 6 hours), oxygen concentration 8%, firing temperature 1400 ° C., maximum temperature holding time 9 hours. Secondary firing was performed below to produce silicon nitride-bonded SiC refractories (Examples 15 to 17, Comparative Examples 16 to 17).
(Component analysis of refractory, measurement of physical properties and evaluation of oxidation resistance)
As in Example A above, the results of component analysis, physical property measurement, and oxidation resistance performance evaluation of the refractory are shown in Table 3 below. Table 3 also shows the results of examining the weight change (oxidized weight change rate) in secondary firing.
（実施例Ｃの考察）
０．０５〜３０００μｍのＳｉＣを６５〜８８質量％、０．０１〜１００μｍの金属Ｓｉを９〜２０質量％使用している実施例１５〜１７では、見掛け気孔率が１０％以下、酸化重量変化率が０．５５以下に抑制されることが確認された。これら実施例１５〜１７では、「曝露中の重量減少率」を６．１８％以下、「浸食深さ」を２９８μｍ以下、「粒子保持性」測定における粘着テープへの付着数３９以下に、各々、抑制することができ、「評価後３点曲げ強度」は、１３８ＭＰａ以上に維持されることが確認された。
０．０５〜３０００μｍのＳｉＣの使用量が６５質量％未満である比較例１６および０．０１〜１００μｍの金属Ｓｉの使用量が６５質量％未満である比較例１７では、何れも、見掛け気孔率が１０％超となり、「曝露中の重量減少率」が９．１３％以上、「浸食深さ」が７９９μｍ以上、「粒子保持性」測定における粘着テープへの付着数が１９６以上となり、「評価後３点曲げ強度」は、７０ＭＰａ以下にまで低下し、上記実施例１５〜１７と比べて、耐酸化性能が劣ることが確認された。
(Consideration of Example C)
In Examples 15 to 17 using 0.05 to 3000 μm of SiC of 65 to 88% by mass and 0.01 to 100 μm of metal Si of 9 to 20% by mass, the apparent porosity is 10% or less, and the oxidized weight change. It was confirmed that the rate was suppressed to 0.55 or less. In these Examples 15 to 17, the “weight reduction rate during exposure” was 6.18% or less, the “erosion depth” was 298 μm or less, and the number of adhesion to the adhesive tape was 39 or less in the “particle retention” measurement. It was confirmed that the “3-point bending strength after evaluation” was maintained at 138 MPa or more.
In Comparative Example 16 in which the use amount of SiC of 0.05 to 3000 μm is less than 65% by mass and Comparative Example 17 in which the use amount of metal Si of 0.01 to 100 μm is less than 65% by mass, the apparent porosity is Was over 10%, “weight loss rate during exposure” was 9.13% or more, “erosion depth” was 799 μm or more, and the number of adhesion to the adhesive tape in the “particle retention” measurement was 196 or more. The “rear three-point bending strength” was reduced to 70 MPa or less, and it was confirmed that the oxidation resistance performance was inferior as compared with Examples 15 to 17 described above.
実施例Ｄ：二次焼成条件が「耐酸化性能評価」に及ぼす影響に関する検討
（製造）
実施例３と同様の原料組成で、原料調合、成形を行い、一次焼成（窒素濃度１００％、１４３０℃、６ｈｒ）行った後、酸素濃度８％、最高温度保持時間１０時間とし、焼成温度は１２００〜１７００℃の間で変化させて条件変更を行いながら、各条件下で二次焼成を行い、上記実施例Ａ〜Ｃと同様の手法で「粒子保持性」を評価した結果、および「（評価前後の比較による）３点曲げ強度の低下率」を算出した結果を図２に示している。
また、実施例３と同様の原料組成で、原料調合、成形を行い、一次焼成（窒素濃度１００％、１４３０℃、６ｈｒ）行った後、焼成温度１４００℃、最高温度保持時間１０時間とし、酸素濃度を２〜１２％の間で変化させて条件変更を行いながら、各条件下で二次焼成を行い、上記実施例Ａ〜Ｃと同様の手法で「粒子保持性」を評価した結果、および「（評価前後の比較による）３点曲げ強度の低下率」を算出した結果を図３に示している。
また、実施例３と同様の原料組成で、原料調合、成形を行い、一次焼成（窒素濃度１００％、１４３０℃、６ｈｒ）行った後、酸素濃度８％、焼成温度１４００℃として、最高温度保持時間を３〜１７時間での間で変化させて条件変更を行いながら、各条件下で二次焼成を行い、上記実施例Ａ〜Ｃと同様の手法で「粒子保持性」を評価した結果、および「（評価前後の比較による）３点曲げ強度の低下率」を算出した結果を図４に示している。
Example D: Study on the effect of secondary firing conditions on "Oxidation resistance evaluation" (manufacturing)
With the same raw material composition as in Example 3, the raw materials were prepared and molded, and after primary firing (nitrogen concentration 100%, 1430 ° C., 6 hours), the oxygen concentration was 8%, the maximum temperature holding time was 10 hours, and the firing temperature was While changing conditions between 1200-1700 degreeC, performing secondary baking on each condition, the result of evaluating "particle retention" by the method similar to the said Example AC, and "( FIG. 2 shows the result of calculating the “decrease rate of 3-point bending strength” by comparison before and after the evaluation.
In addition, with the same raw material composition as in Example 3, the raw material was prepared and molded, and after primary firing (nitrogen concentration 100%, 1430 ° C., 6 hours), the firing temperature was 1400 ° C., the maximum temperature holding time was 10 hours, oxygen As a result of performing secondary firing under each condition while changing the concentration between 2 to 12% and evaluating the “particle retention” in the same manner as in Examples A to C, and FIG. 3 shows the result of calculating “the rate of decrease in three-point bending strength” (by comparison before and after evaluation).
Also, with the same raw material composition as in Example 3, the raw material was prepared and molded, and after primary firing (nitrogen concentration 100%, 1430 ° C., 6 hours), the oxygen concentration was 8% and the firing temperature was 1400 ° C., and the maximum temperature was maintained. As a result of performing secondary firing under each condition while changing the conditions between 3 and 17 hours, and evaluating the “particle retention” in the same manner as in Examples A to C above, FIG. 4 shows the results of calculating the “decrease rate of the three-point bending strength” (by comparison before and after the evaluation).
（実施例Ｄの考察）
酸素濃度４〜１０％、焼成温度１３００〜１６００℃、焼成時間５〜１５時間で二次焼成を行うことにより、粒子保持性が改善され、強度低下が抑制されることが確認された。
(Consideration of Example D)
It was confirmed that by performing secondary firing at an oxygen concentration of 4 to 10%, a firing temperature of 1300 to 1600 ° C., and a firing time of 5 to 15 hours, particle retention was improved and strength reduction was suppressed.
Claims (8)
見掛け気孔率が１０％以下であり、
化学組成として、Ａｌを０．２５〜２．４質量％かつＢを１．５超〜８．５質量％含有する
ことを特徴とする複合耐火物。 A composite refractory in which a silicon nitride-bonded SiC refractory in which silicon carbide is bonded with silicon nitride and / or silicon oxynitride is formed with a SiO 2 glass coating,
The apparent porosity is 10% or less,
A composite refractory comprising, as a chemical composition, 0.25 to 2.4% by mass of Al and more than 1.5 to 8.5% by mass of B.
見掛け気孔率が１０％以下であり、
該複合耐火物の表面から少なくとも０．５ｍｍ深さの部分に、化学組成として、Ａｌを０．２５〜２．４質量％かつＢを１．５超〜８．５質量％含有することを特徴とする複合耐火物。 A composite refractory in which a silicon nitride-bonded SiC refractory in which silicon carbide is bonded with silicon nitride and / or silicon oxynitride is formed with a SiO 2 glass coating,
The apparent porosity is 10% or less,
In a portion at least 0.5 mm deep from the surface of the composite refractory, the chemical composition contains 0.25 to 2.4% by mass of Al and more than 1.5 to 8.5% by mass of B. Composite refractory.
ＳｉＣを６５〜８８質量％、Ｓｉを９〜２０質量％含有させた原料を混合し、窒素雰囲気下での一次焼成後、この一次焼成により得られた焼成体の表面に、固形分として、Ｂ４Ｃを２．５〜１５質量％、Ａｌ２Ｏ３を０．５〜１０質量％含有させたスラリーを用いてコーティング処理を行い、その後、酸素濃度４〜１０％の酸素雰囲気下で二次焼成を行うことを特徴とする複合耐火物の製造方法。 A method for producing a composite refractory according to claim 2, comprising:
A raw material containing 65 to 88% by mass of SiC and 9 to 20% by mass of Si is mixed, and after primary firing in a nitrogen atmosphere, the surface of the fired body obtained by the primary firing has B as a solid content. 4 C is coated with a slurry containing 2.5 to 15% by mass of Al and 0.5 to 10% by mass of Al 2 O 3 , and then subjected to secondary treatment in an oxygen atmosphere having an oxygen concentration of 4 to 10%. A method for producing a composite refractory, characterized by firing.
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